CN103846021B - A kind of separation membrane material its synthesis and application - Google Patents

A kind of separation membrane material its synthesis and application Download PDF

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CN103846021B
CN103846021B CN201210540764.0A CN201210540764A CN103846021B CN 103846021 B CN103846021 B CN 103846021B CN 201210540764 A CN201210540764 A CN 201210540764A CN 103846021 B CN103846021 B CN 103846021B
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membrane material
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CN103846021A (en
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曹义鸣
蒋璨
康国栋
李萌
刘丹丹
袁权
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention is about a kind of novel high intensity, high selective separation membrane material and synthetic method.This synthetic method is relatively low to the purity requirement of raw material, greatly reduces the cost of the polymer synthesized, and the synthesis of polymer is main in two steps, and the first step is polycondensation reaction, and second step is substitution reaction.This membrane material be introduce isobutyl group or normal-butyl on the polymer chain by AB type polybenzimidazoles based on, the method is by the membrane material gone out synthesized by the ratio of the different substituent group of regulation, it is possible to obtain higher gas separating property.This membrane material synthesis condition is gentleer, and process is simple, and the polymeric material synthesized has higher heat-resistant stability and resistance to acids and bases and higher mechanical strength, may be used for the fields such as gas separation membrane, fuel cell.

Description

A kind of separation membrane material its synthesis and application
Technical field
The present invention relates to a kind of new polymers membrane material and synthetic method, this material may be used for gas and separates Film, the field such as fuel cell.
Background technology
Membrane separation process is higher than conventional separation techniques separation efficiency, more energy efficient, more environmentally friendly so that membrance separation becomes Solve to alleviate lack of energy and the new and high technology of environmental pollution a few days ago.Gas in application of membrane separation technology separates Film is that application surface is relatively wide, is also the bigger novel film kind in market simultaneously.Due to film gas separation skill Art has the advantages such as using method is simple, quick, energy-efficient, thus receives much attention and adopt, by It is widely applied to the fields such as chemical industry, electronics, the energy and environmental protection.In decades, gas separation membrane is applied at it During, the most progressively replace or improve the most traditional absorption technique, such as some polymeric film catalysts and Methane and carbon dioxide in method separating natural gas associated with absorption replaces traditional absorption；In gymnasium etc. Need the built-in separation film adding air separation and concentration oxygen in place of sufficient oxygen.As a unique separation Technology, it has become as modern industry, and especially high, precision and frontier end technical industry, as electronics, science are ground Study carefully and one of indispensable important means ensureing product quality in the field such as space flight.Owing to it is superior Characteristic and be widely applied scope, during the most alive limitans market overall is constituted, gas separation membrane product accounts for There is critically important share.
Compared with traditional gas separate mode, the principal character of gas separation membrane shows following points:
(1) cortex of anisotropic membrane is the thinnest, it is possible to achieve the bigger flux of gas, reduces gas owing to being inhaled The membrance separation receiving loss (2) gas caused can be carried out under less pressure reduction, reduces energy consumption；(3) poly- The desorbing problem that there is not absorbent in absorption operation when separating membrance separation that laminate material is made, decreases energy Consumption, and secondary pollution will not be produced；
Currently mainly membrane material is also not quite similar because of concrete distinct, the preparation method of synthesis and film, closes One-tenth condition also has dividing of harsh and gentleness.The monomer of synthesis membrane material is different, can also two kinds with auto polymerization The polymerization of above monomer or copolymerization, the degree of polymerization of the polymer synthesized, molecular weight is the most variant, gives polymerization The popularity of thing synthesizes and expands its application and brings adverse effect.People's polymer to having synthesized Requirement according to oneself carries out modification, these remodeling means include cross-linking, replace, are grafted, are blended, Copolymerization, adulterate organic inorganic nano-particle or soda acid etc..Change after wherein substitution reaction is Macroscopic single crystal One of property important means making novel high polymer or derivant, it is at reagent bag by polymer Include hydrogen bond reagent, ionization reagent and substituting agent.Shape after a certain atom such as nitrogen atomic ion in polymer Become alkyl on electronegative material, halogenated hydrocarbon or other halogenated compounds with the form of positive charge and Nitrogen is born compound and is combined.The polymer synthesized under certain condition has certain molecular weight, and polymer can With film forming well.Nineteen ninety Michael in United States Patent (USP) US 4898917 to polybenzimidazoles Derivant has carried out roundup.He points out that many conditions of polybenzimidazole derivatives synthesis of planting are with corresponding Substituent group group.Describe the conjunction of the derivant of the polybenzimidazoles of biphenyl group connection imidazole group more Become.The first step of synthesis is also first to synthesize polybenzimidazole polymer, and second step is between 70-150 DEG C The ionizing of the pyridine nitrogen atom of polybenzimidazoles, followed by through the reaction of room temperature to 40 DEG C, alkyl, or Person's alkyl containing inorganic elements replaces hydrogen cation and generates the derivant of polybenzimidazoles.Add different amounts of Halogenated hydrocarbon or the halogenated hydrocarbons containing inorganic elements, the molecular weight of the derivant of the polybenzimidazoles of generation is not to the utmost Identical, the separating property separating film being made from is the most variant.But the densification prepared by this polymer From the point of view of the intrinsic separating property of film, the infiltration coefficient of gas is the most relatively low, limits its application.
A kind of novel polybenzimidazoles, AB type polybenzimidazoles derivant synthesis pertinent literature then The most limited, based on some researchs it is recognised that the free volume of the derivant of the polybenzimidazoles of AB type is permissible Bigger than the polybenzimidazoles of common type (connect imidazole group is biphenyl group), say, that by AB The flux of the film that type polybenzimidazole derivatives is made can be bigger, more suitable for use in the separation of some gas pair Aspect.
Due to the variation of halides reagent, the hydrogen atom on nitrogen-atoms can by number of types of alkyl, with And the hydro carbons etc. containing inorganic elements such as element silicon replaces, we can be according to gas design molecule knot to be separated Structure, sets group to be introduced.
It addition, the film limitednumber that the derivant of some the AB type polybenzimidazoles synthesized is made, the fewest The film that number different materials is made is used as gas separation aspect.
As a kind of good gas separation membrane material, isobutyl alkyl replaces AB type polybenzimidazole membrane and has good Good hot property and mechanical strength, acid-proof alkaline, significantly widened its range of application, may be used for liquid The fields such as body separates, and gas separates, fuel cell.
Summary of the invention
It is an object of the invention to attempt a kind of novel high intensity and Thief zone coefficient and high separation membrane material Synthetic method.This method uses two-step method to synthesize, and the first step is premise and the basis of second step, and second The alkylating reagent of step is varied.The hydrogen of dense film prepared with the membrane material of synthesis is to carbon dioxide Separation reach 6.3, can adding different halides when synthesis, to synthesize substituent group colourful Copolymers etc., can synthesize the membrane material that applicable various gases separate.
In order to achieve the above object, the present invention uses two-step method first to synthesize it after AB type polybenzimidazoles Ionizing, is incorporated into isobutyl alkyl in atom N.
A kind of separation membrane material, containing special groups R1,R2AB type polybenzimidazole derivatives in, its molecule Structural formula is as follows:
AB type polybenzimidazole derivatives
The wherein integer in m=1～100, the integer in n=100～0, m+n >=40；
R1,R2Being the group being connected with pyridine nitrogen atom, they are to be connected to AB type polyphenyl also by substitution reaction On the side chain of imidazoles, R1For normal-butyl alkyl or isobutyl group alkyl, R2For the hydrocarbon that carbon atom quantity is 1～20 Base or the alkyl that carbon number is 1～20 containing 1-3 inorganic silicon element.
Synthetic method: AB type polybenzimidazole derivatives is to be obtained by alkylated reaction by AB type polybenzimidazoles Arrive；I.e. AB type polybenzimidazoles, in alkylated reaction medium, adds ionization reagent and substituent group reagent Obtain through reaction.
AB type polybenzimidazoles obtains through condensation polymerization reaction；
Polycondensation reaction: comprise a kind of monomer self-polymerization of two amino and a carboxyl between 120-200 DEG C, React under the effect of catalyst and dehydrant 1-5 hour and polyreaction occurs；
The structural formula of monomer is:
3,4-diaminobenzoic acids.
Alkylated reaction medium comprises dimethyl sulfoxide, dinethylformamide, N,N-dimethylacetamide, Oxolane, acetonitrile, potassium nitrate, ethyl acetate, one or two or more kinds in dichloromethane；AB type gathers Benzimidazole is 1:3～1:10 with the interpolation molar ratio of alkylated reaction medium.
Ionization reagent sodium hydride, lithium hydride, hydrofining, potassium carbonate, sodium carbonate, lithium carbonate, bicarbonate Sodium, potassium bicarbonate, aluminium sesquioxide, magnesium oxide, one or two or more kinds in calcium oxide.
Substituent group reagent is containing R1,R2The halides of group, the halogen element in halides is Cl or Br；
Containing R1The halides of group is halo normal butane or halo iso-butane；
Containing R2The halides of group be halo carbon number be hydrocarbon or halo element Han inorganic silicon of 1～20 The hydrocarbon that carbon number is 1～20.
AB type polybenzimidazoles is 2:1～1:3 with the interpolation molar ratio of alkylating reagent.
Ionization reagent is 1:1～1:5 with the interpolation molar ratio of substituent group reagent.
AB type polybenzimidazoles is 1:1～1:2 with the interpolation molar ratio of ionization reagent.
The present invention also provides for the application of a kind of described membrane material, is specially and membrane material is applied to hydrogen/titanium dioxide Carbon, oxygen/nitrogen, carbon dioxide/methane, titanium dioxide carbon/nitrogen gas, hydrogen/nitrogen, or hydrogen/methane Separate.
Present invention have the advantage that synthesis is simple, require relatively low to monomer, various monomers are analytical pure Grade, purity is no more than 99%, easy to operate, it is simple to industrialization is amplified；Employing two-step method synthesizes, permissible Arbitrarily regulating ratio and the kind of substituent group, a kind of substituent group, multiple substituent group, the two is again the most solely Vertical.Constituent adjustment is convenient, and it is high that separation film prepared by the method has intensity, and infiltration coefficient is big and separates hydrogen The advantage high to other gas separation coefficients.
Detailed description of the invention
(1) by catalyst, dehydrant and corresponding monomer add flask together with catalyst, and solution is at 100-200 In the range of occur condensation reaction；
(2) ionizing of polymer: take a certain amount of above-mentioned polymer, add a certain amount of ionization reagent With reaction medium (serving as hydrogen bond reagent in this reaction), there is ionizing in polymer in the range of 80-200 DEG C Reaction, the nitrogen-atoms on imidazoles becomes positively charged nitrogen；
(3) a certain amount of halides is added, N in imidazoles+Accept from the alkyl in halides or other bases Group forms substituted type derivant, and imidazol ion solution and halides are reacted 5-72 hour at 25-80 DEG C.
Using hydrogen, nitrogen, oxygen, methane in the present invention, carbon dioxide test separates the separating property of film.
Test process is as follows: after whole osmotic system evacuation, pour in gas tank by gas to be measured, so After by except the whole pipeline evacuation of air accumulator, then open feed valve, after rate stabilization to be infiltrated, stop Gather data.Penetration equipment used is laboratory self-control, the test correction of osmotic cell parameter standard film.
Gas permeability coefficient: P
Separation separation:
α A / B = P A P B
In formula:
P is the infiltration coefficient (Barrer) of gas；
L is the thickness (cm) of film；
V is the volume (cm of inventory of gas tank3)；
A is the effective film area (m separating film2)；
Dp/dt is the pressure (Torr/s) over time of osmotic cell infiltration gas.
Embodiment 1:
A, by 2g 3,4-diaminobenzoic acid (DABA) and 50g polyphosphoric acids join in flask, will Reaction temperature brings up to 140 DEG C, treats that DABA is completely dissolved, and reaction temperature is increased to 170 DEG C, monomer pre-polymerization Close, then reaction temperature brings up to 200 DEG C, after reacting 5 hours, the solution of reaction is poured into stirring go from In sub-water, obtain the fibrous material of dead color.
B, puts into vacuum drying oven 110 DEG C and is dried after fully being washed by fibrous polymer deionized water；
C, after above-mentioned polymer A Type B polybenzimidazoles 1.5g is added there-necked flask, adds 80ml successively Dimethyl sulfoxide, 0.615g dry sodium hydride, after 170 DEG C of reactions 5 hours, add 5ml dimethyl sub- Sulfone and the mixed liquor of 2.141g isobutane bromide, after 40 DEG C of reactions 24 hours, by slow for the solution obtained Pour in deionized water, then the solid that obtains is dissolved with formic acid after drying and be dried in case casting film after purifying.
D, makes casting solution by above-mentioned polymer, solvent volatilize 10 hours after film forming.
The gas separating property that test obtains dense film is as follows: 35 DEG C, under 2MPa, hydrogen gas permeation coefficient is 11.4barrer, hydrogen is up to 6.3 to the separation of carbon dioxide, and the separation of nitrogen is up to by hydrogen 212.9.This film (thickness: 30 μm) can stand 40 atmospheric pressure and more than.
Embodiment 2:
Adjust the kind of monomer of synthetic polymer, in above-mentioned reactions steps c: add 0.615g sodium hydride and 2.141 bromination of n-butane, remaining condition is the most same as in Example 1.
The performance that test obtains film is as follows: 35 DEG C, under 2MPa, hydrogen gas permeation coefficient is 15.4barrer, hydrogen Gas is 2.3 to the separation of carbon dioxide, and hydrogen is up to 50.6 to the separation of nitrogen.This film is (thick Degree: 30 μm) can stand 40 atmospheric pressure and more than.
Embodiment 3:
Adjust the ratio of monomer of synthetic polymer, above-mentioned reactions steps c is added 0.923g sodium hydride and 2.141g isobutane bromide and 1.071g bromination of n-butane (isobutane bromide and bromination of n-butane mol ratio are 2: 1), remaining condition is the most same as in Example 1.
The performance that test obtains film is as follows: 35 DEG C, under 2MPa, hydrogen gas permeation coefficient is 12.9barrer, hydrogen Gas is 5.0 to the separation of carbon dioxide, and hydrogen is up to 117.2 to the separation of nitrogen.This film is (thick Degree: 30 μm) can stand 40 atmospheric pressure and more than.
Embodiment 4:
After AB type polybenzimidazoles 2.41g is added there-necked flask, add the dimethyl sulfoxide of 160ml successively, 1.23g dry sodium hydride, after 170 DEG C are reacted 5 hours, adds 25ml dimethyl sulfoxide and 2.141g bromo The mixed liquor (isobutane bromide and bromination of n-butane mol ratio are 1:1) of iso-butane and 2.141g bromination of n-butane, C, Step d are the most same as in Example 1.
The performance that test obtains film is as follows: 35 DEG C, under 2MPa, hydrogen gas permeation coefficient is 12.4barrer, hydrogen Gas is up to 3.9 to the separation of carbon dioxide, and hydrogen is up to 80.5 to the separation of nitrogen.This film is (thick Degree: 30 μm) can stand 40 atmospheric pressure and more than.

Claims (9)

1. a separation membrane material, it is characterised in that: containing special groups R1,R2AB type polybenzimidazoles In derivant, its molecular structural formula is as follows:
The wherein integer in m=1～100, the integer in n=100～0, m+n >=40；
R1,R2Being the group being connected with pyridine nitrogen atom, they are to be connected to AB type polyphenyl also by substitution reaction On the side chain of imidazoles, R1For normal-butyl alkyl or isobutyl group alkyl, R2For the hydrocarbon that carbon atom quantity is 1～20 Base.
2. the synthetic method of the membrane material described in a claim 1, it is characterised in that:
AB type polybenzimidazole derivatives is obtained by alkylated reaction by AB type polybenzimidazoles；I.e. AB type polybenzimidazoles, in alkylated reaction medium, adds ionization reagent and substituent group reagent through reaction Obtain.
3. according to the synthetic method described in claim 2, it is characterised in that: AB type polybenzimidazoles is through contracting Polyreaction obtains；
Polycondensation reaction: comprise a kind of monomer self-polymerization of two amino and a carboxyl between 120-200 DEG C, React under the effect of catalyst and dehydrant 1-5 hour and polyreaction occurs；
The structural formula of monomer is:
4. according to the synthetic method described in claim 2, it is characterised in that: alkylated reaction medium comprises two Methyl sulfoxide, dinethylformamide, N,N-dimethylacetamide, oxolane, acetonitrile, potassium nitrate, Ethyl acetate, one or two or more kinds in dichloromethane；AB type polybenzimidazoles and alkylated reaction medium Interpolation molar ratio be 1:3～1:10.
5. according to the synthetic method described in claim 2, it is characterised in that: ionization reagent is sodium hydride, Lithium hydride, hydrofining, potassium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, three oxidations two Aluminum, magnesium oxide, one or two or more kinds in calcium oxide.
6. according to the synthetic method described in claim 2, it is characterised in that: substituent group reagent is containing R1,R2 The halides of group, the halogen element in halides is Cl or Br；
Containing R1The halides of group is halo normal butane or halo iso-butane；
Containing R2The halides of group be halo carbon number be the hydrocarbon of 1～20.
7. according to the synthetic method described in claim 2, it is characterised in that: ionization reagent tries with substituent group The interpolation molar ratio of agent is 1:1～1:5.
8. according to the synthetic method described in claim 2, it is characterised in that: AB type polybenzimidazoles and ion The interpolation molar ratio changing reagent is 1:1～1:2.
9. the application of membrane material described in a claim 1, it is characterised in that: this membrane material is applied to hydrogen / carbon dioxide, oxygen/nitrogen, carbon dioxide/methane, titanium dioxide carbon/nitrogen gas, hydrogen/nitrogen, or hydrogen The separation of/methane.
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CN106995581B (en) * 2017-05-26 2018-11-23 山东宇世巨化工有限公司 A kind of polybenzimidazoles, the combined modified phenolic resin foam of carboxy nitrile rubber and preparation method thereof
CN111085088B (en) * 2018-10-23 2022-04-05 中国石油化工股份有限公司 Polyacrylonitrile fiber for gas filtration and preparation method and application thereof

Citations (5)

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Publication number Priority date Publication date Assignee Title
US4898917A (en) * 1987-09-11 1990-02-06 Hoechst Celanese Corporation N-substituted polybenzimidazole polymer
CN1848504A (en) * 2005-04-05 2006-10-18 中国科学院大连化学物理研究所 Composite proton exchange membrane for high-temperature fuel battery and producing method thereof
CN101768270A (en) * 2010-01-12 2010-07-07 山东理工大学 Method for protecting amino end groups in polybenzimidazole high-molecular material
CN102084529A (en) * 2008-06-16 2011-06-01 埃尔科马克斯薄膜有限责任公司 Use of a material imparting proton conductivity in the production of fuel cells
CN102299351A (en) * 2010-06-25 2011-12-28 中国科学院大连化学物理研究所 Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4898917A (en) * 1987-09-11 1990-02-06 Hoechst Celanese Corporation N-substituted polybenzimidazole polymer
CN1848504A (en) * 2005-04-05 2006-10-18 中国科学院大连化学物理研究所 Composite proton exchange membrane for high-temperature fuel battery and producing method thereof
CN102084529A (en) * 2008-06-16 2011-06-01 埃尔科马克斯薄膜有限责任公司 Use of a material imparting proton conductivity in the production of fuel cells
CN101768270A (en) * 2010-01-12 2010-07-07 山东理工大学 Method for protecting amino end groups in polybenzimidazole high-molecular material
CN102299351A (en) * 2010-06-25 2011-12-28 中国科学院大连化学物理研究所 Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof

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